Amine-modified thermoplastic phenolaldehyde resins and method of making same



g- 1961 M. DE GROOTE 2,997,460

AMINEI-MODIFIEZD THERMOPLASTIC PHENOL-ALDEHYDE RESINS AND METHOD OF MAKING SAME Original Filed Aug. 6, 1954 OH OH OH OH H H H 1 C C C H H H R R R R F|G.I

OH OH OH 1 H H J C C H H HBCC-CH 3 R R H H C C H H T OH OH OH FIG.2

OH OH OH OH 2 2 *e H H H R R R H3C-C*CH3 F|G.3 OH

OH OH OH I H H 1 C C H H HsC-C-CHa H H c c T H H OH OH OH 2,997,460 AMINE-MODIFIED THERMOPLASTIC PHENOL- ALDEHYDE RESINS AND METHOD OF MAK- ING SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Wilmington, Del., a corporation of Delaware Original application Aug. 6, 1954, Ser. No. 448,173,

now Patent No. 2,854,415, dated Sept. 30, 1958. Dizisdleglgnd this application Apr. 10, 1957, Ser. No.

5 Claims. (Cl. 2v60-51) This application is a division of my copending application Serial No. 448,173, filed August 6, 1954.

My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

Attention is directed to my co-pending applications, Serial Numbers 288,742, through 288,746, inclusive, filed May 19, 1952, all now abandoned. The first of said co-pending applications relates to a process of condensing certain phenol-aldehyde resins derived from phenols having a functionality not greater than 2, therein and hereinafter described in detail, with certain basic nonhydroxylated secondary monoamines, also therein described in detail, and formaldehyde.

The second application is similar to the first except that the monoamines employed as reactants are hydroxylated instead of being nonhydroxylated. The third application is similar to the first one insofar that nonhydroxylated polyamines are employed as reactants. The fourth application is concerned with hydroxylated polyamines as reactants and the last application is concerned with amines having a cyclic amidine group in the reactant regardless of whether it is hydroxylated or not.

The present application is differentiated from the aforementioned five applications in that the resin employed instead of being difunctional towards formaldehyde is tetrafunctional towards formaldehyde. Stated another way this invention is concerned with a process of condensing certain phenol-aldehyde resins which are tetrafunctional towards formaldehyde and are hereinafter described in detail, with certain basic secondary amines, also hereinafter described in detail, and formaldehyde.

The manufacture of oXyalkylation-susceptible, fusible, organic solvent-soluble water-insoluble, low-stage phenol aldehyde resins having an average molecular weight cor responding to at least 3 and not over 6 phenolic nuclei per resin molecule and obtained without the use of a bisphenol have been described in a large number of patents including among others, US. 2,499,367, dated March 7, 1950, to De Groote and Keiser. Similarly oXyalkylation-susceptible, fusible, organic solvent soluble, waterinsolble phenol aldehyde resin derived by reaction be tween an aldehyde having but one functional group reactive with bisphenol and a difunctional bisphenol reactive towards aldehydes has been described in the US. Patent No. 2,564,191, dated July 14, 1951.

As far as I am aware there is no suitable description of a phenol aldehyde resin derived from two classes of phenols, one being a phenol of the formula ice in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; the other being a tetrafunctional bisphenol; the ratio of the two classes of phenols employed being so as to contribute one bisphenol residue per resin molecule and particularly as employed in the present invention as a reactant. The nature of the condensate as obtained by the present manufacturing process is best understood by referring to comparable products derived from a difunctional resin rather than a tetrafunctional resin. In this instance functionality refers to reactivity toward formaldehyde or its equivalent.

For purpose of illustration it may be simpler to divert momentarily to the products described in the five aforementioned co-pending applications, Serial Nos. 288,742 through and including 288,746, inclusive and for sake of simplicity to the first one, i.e., Serial No. 288,742, in which the amine reactant is a nonhydroxylated monoamine. For purpose of simplicity the invention described in said co-pending application, Serial No. 288,742 may be exemplified by an idealized formula, as follows:

R R n in which R represents a hydrocarbon substituent generally having 4 and not over 18 carbon atoms but most preferably not over 14 carbon atoms and It generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., free from hydroxyl radicals. The only limitation is that the radical should not be a negative radical, which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. Needless to say, the two occurrences of R may jointly represent a single divalent radical instead of two monovalent radicals. This is illustrated by morpholine and piperidine. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R; contains one or more oxygen :atoms, another eifect is introduced, particularly another hydrophile effect.

Such condensates, i.e., the condensates of Serial No. 288,742, are obtained from conventional phenol-aldehyde points of reactivity towards formaldehyde.

resins. It is well known that one can readily purchase on the open market, or prepare fusible, organic solventsoluuble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH {ll-[071510 H H R R n R In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 to 12 units, particularly when the resin is subjected 15 to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i.e., n varies from 1 to 4; R represents a hydrocarbon substituent, generally an alkyl radi cal having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Reference is now being made to the accompanying drawing in which FIGURE 1 depicts a conventional resin of the kind referred to in my co-pending applications Serial Nos. 288,742, through 288,746, dated May 19, 1952. In the drawing R simply denotes an alkyl radical having 4 to 24 carbon atoms and the arrows indicate two Needless to say, such resins can be obtained from any difunctional phenol and not necessarily a parasubstituted phenol.

The other figures in the drawing, to wit, 2, 3 and 4, depict in a similar manner resins of the kind herein employed in which one tetrafunctional bisphenol has entered into the resin structure and again the letter R has its prior significance and again the arrows indicate four points of reactivity. Obviously ortho substituted phenols could be employed as well as parasubstituted phenols.

It is obvious that with difunctional resins the most one could combine is one or two moles of a suitable amine whereas in the use of resins herein described one could substitute not only one or two but as many as three or four and thus obtain products of an entirely different character and particularly have an increased hydrophile property in many instances.

Reverting again to what is said in the five co-pending applications previously referred to, and particularly to Serial No. 288,742, reference is made to the text which describes other products of reaction which appear in the cogeneric mixture resulting from reaction between the resin, the secondary amine and formaldehyde. The reference is as follows:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

OH OH OH OH OH OH aloe ijegel'flril H H H H H R R n R R R n R When a difunctional resin is replaced by a tetrafunctional resin in light of what has been said it becomes apparent, and particularly so when the amount of formaldehyde and the amount of amine is increased to 3 or 4 moles per mol of resin, that a much more complicated and much different structure results. Furthermore, to the extent that a molecular weight determination or an approximation thereof can be made the indications point to distinctly higher molecular weights than in the case of difunctional resins. In any event, the condensates so obtained are different in character and for some purposes particularly after oxyalkylation with ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide are especially effective for the resolution of petroleum emulsions. Indeed, in many instances the oxyalkylation derivatives are distinctly more effective than the comparable products derived from condensates in which difunctional resins are used.

For purpose of convenience what is said hereinafter will be divided into five parts:

Part 1 is concerned with phenol-aldehyde resin suitable for condensation;

Part 2 is concerned with suitable secondary amines which can be employed in conjunction with the resins in the condensation procedure;

Part 3 is concerned with the condensation procedure as such;

Part 4 is concerned with the uses of the condensates for the resolution of petroleum emulsions; and

Part 5 is concerned with uses for the condensates for purposes other than demulsification, and particularly for their use as initial raw materials which are subjected to oxyalkylation.

PART 1 This is concerned with the preparation of phenolald'ehyde resins of the kind previously referred to, i.e., oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resins having an averagemolecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being derived by reaction between an aldehyde having not over 8 carbon atoms and reactive towards two classes of phenols, one being (A) a phenol of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; the other being (B) a tetrafuctional bisphenol; the ratio of the two classes of phenols employed being so as to contribute one bisphenol residue per resin molecule.

The method employed for preparation of such resin is identical with that described in regard to the preparation of resins obtained solely from difunctional phenols as referred to in U.S. Patent No. 2,499,367 or resins obtained from difunctional bisphenols as described in US. Patent No. 2,564,191.

In either event one can prepare the resin with or without the use of a catalyst. The catalyst may be acid or basic. An acid catalyst such as sulfonic acid is preferred. In the present instance the difunctional phenol as differentiated from the bisphenol may have as many as 24 carbon atoms substituted in either the ortho or para position. For practical purposes those having 4 to 14 carbon atoms in the side chain are most suitable. There may or may not be a meta-substituent present. The ordinary phenols used are butylphenol, amylphenol, hexylphcnol, octylphenol, no-nylphenol, decylphenol, dodecylphenol, and tetradecylphenol. Generally, these are para substituted phenols and have no substituent in the meta position. Substituents may vary in structure as for example, the butyl group may be secondary or tertiary and the amyl group may also be secondary or tertiary. Such resins can be prepared with or without the use of a solvent, but for most purposes it is preferable to have a solvent present. The aldehyde used may be any aldehyde having not over 8 carbon atoms and particularly formaldehyde, acetaldehyde, propionaldehyde or butyraldehyde.

Resins of the kind herein described, i.e., tetrafunctiona1 resins having 3 to 6 phenolic nuclei, one of which is a bisphenol nucleus per resin molecule have not been suitably described but the method of manufacture used in connection with the preparation of other comparable resins is entirely suitable.

For instance see US. Patent No. 2,499,368, dated March 7, 1950, to De Groote andKeiser. Resins can be made using an acid catalyst or basic catalyst or a catalyst showing neither acid nor basic properties in the ordinary sense, or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reactions described involving amines proceeded more rapidly in the presence of a small amount of free base. The amount may be as small as a 200th of a percent and as much as a few tenths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral, except for the basicity of the amino groups, of the added reactant in the second step.

In preparing resins one does not get a single polymer, i.e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, "the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5, or 5.2.

In the present instance one follows such well-known procedure but makes a mixture of part of the bisphenol with 2, 3, 4 or 5 parts of a difunctional phenol. The difunctional phenol employed may need not be necessarily the same and for that matter one could employ both ortho-substituted and para-substituted phenols. Resinification is carried along until the usual methods of molecular weight determination indicates a molecular weight corresponding to a combination of the tetrafunctional bisphenol with an equivalent amount of difunctional phenols, for instance a molecular weight corresponding to one mole of a tetrafunctional phenol and 2 moles of a difunctional phenol or a l and 3 combination or a 1 and 5 combination.

Bisphenols are well known and the most common example, and in fact the only one produced on a large commercial scale, is bisphenol A which is dihydroxydiphenyb dimethylmethane. The word bisphenol is used in the same sense as it is used in US. Patent No. 2,506,486, dated May 2, 1950 to Bender, et a1. As stated in that patent:

By terms diphenol, diphenylol, bisphenol, and dihydroxydiphenyl as used herein is meant the dihydroxydiphenylmethanes, including the isomers, homologs and substituted dihydroxydiphenylmethane compounds all as set forth above. Unless the positions of the phenolic hydroxyl groups are otherwise specifically indicated, it is to be understood that they are in the 4,4 (para, para) posi' tions on the phenyl rings.

In the instant case, however, bisphenols are limited to tetrafunctional bisphenols and for practical purposes this means bisphenols in most instances in which all four ortho groups are not substituted. Examples of such bisphenols are the following:

Comparable bisphenols can be obtained using meta cresol as the initial reactant instead of phenol. A variety of other comparable diphenols are well-known as for example a diphenol of the following formula where R is a small alkyl group having not over 8 carbon atoms. For practical purposes, however, the most satisfactory bisphenol is bisphenol A. Equally satisfactory is bisphenol B which has the following formula Some other comparable bisphenols are available.

At least one and in some instances two meta-substitued methyl radicals appear. As to other bisphenols some of which are suitable for the instant purpose, i.e., are tetrafunctional see US. Patents Nos. 2,482,728, 2,575,558, 2,626,939, 2,530,353.

As to the preparation of resins one can use the procedure as outlined in Example 1a in aforementioned US. Patent No. 2,499,370. One can use any of the difunctional phenols described in said patent and furthermore one can use any of the aldehydes employed and also any of the catalysts and any of the solvents. For purpose of convenience, what is said hereinafter will be limited largely to the use of formaldehyde particularly the 37% formaldehyde solution and the use of an acid catalyst along with xylene or similar solvent. Using the same procedure as described in connection with example la in aforementioned US. Patent No. 2,499,370 and using approximately 0.6% of monoalkyl (C -C principally C -C benzene monosulfonic acid sodium salt in combination with 1% of HCl as a catalyst, a number of suitable resins have been prepared. Similarly the same procedure but employing 1% of diamylnaphtalene sulfonic acid as a catalyst based on the weight of the reaction mass a number of resins were prepared as described in Table I and Table II immediately following:

TABLE I Diamyl- Ex. Bis- Amount, Ditunetional Amount, naphtha- Amount, Amount, No. phegrams phenol grams lene sul- Aldehyde grams Solvent grams nol fonie acid A 114 p-Tert-amyl.. 328 6. 3 Form. 37% sol 203 High boil. 9.1'0111. pet. $01.. 461 A d 328 6.2 do 178 d 474 A 328 8.2 604 A 197 4.8 356 A 246 5. 2 389 A 273 5.1 378 A 328 6 443 A 164 5.3 414 A 164 3.0 256 A 164 3.3 292 A 164 3.4 303 A 164 6.2 288.5 A 164 7.2 333 A 164 7.4 357 A 164 3.3 315 A 164 3. 5 365 A 144 3. 6 243 A 76 p-Teit-butyl. 200 4. 1 300 A 76 Octyl-phenoL 275 4. 9 376 B 81 Nonyl-phenol. 295 5. 396 O 85 o-Tert-amyl... 219 6. 2 315 D 67 p Tert-amyL" 219 4. 1 299 Bisphenol A is p,p-dihydroxy diphenyl dimethyl methane.

Bisphenol B is the comparable derived from ethyl methyl ketone instead of dimethyl ketone. Bisphenol C is comparable to bisphenol A but derived from meta-cresol instead of phenol. Bisphenol D is o,o-dihydroxy diphenyl methane.

TABLE II Molal Mol Max. ratio oi ratio of temp. Ex. bisphewater during Hardness Theo. No. nol to out based resinifi- Color (solv. free molcc. Remarks (see note D) difunct on aldecation, basis) weight 1 phenol hyde 1 C. to aldeh 1.02 150 Ainlllier black Hard 954 The 50% solution is a soft solid.

s 0.959 150 do 954 (See note A.) 0. 994 134 Black (red (See note B.) 0.906 155 Araberk) 990 2.7 moles H1O liber. per mole bisphenol.

ac 0.974 150 Black-purple 768 Viscosity at 95 C.=226 cps. 1.0 155 Black-red Viscosity=160 cps. at 80 0. 0. 96 150 Black-brown 0.98 154 Dark purple." 0.756 146 Dark brown... H (See note 0.) V 0. 825 145 o... Hi0/bisphenol=3.65 moles, reaction time 17.5 hrs. 0.975 145 Dark amb H O/bisphenol=4.4. 0. 71 149 Brown (dark) H O/bisphenol=3.55, reaction time 17.5 hrs. 0.957 Dark brown... HrO/bisphenol=4.77. :5 0. 845 H2O/bisphen0l=4.22, reaction time 17.5 hrs. :5 0. 977 H:O/bisphenol=0.984. :5 0. 956 HtO/bisphenol=4.77. :5 0. 833 HO/bisphenol=4.17. :5 0. 833 Do. :5 0.85 HrO/bisphenol=4.18. :5 0. 8 HzO/bisphenol=4. :5 0.8 Do. :5 0. 867 Very hard resin.

Note A-d50% solution is very viscous, but not as much as when HCHO is 5 moles. The viscosity of 50% solution at 100 C.=2-2 cps. was use Note B-Grosslinkage occurred during dehydration HCHO to phenol ratio (1:1.1) is probably too high.

Note O-HO/bisphenol3.78 moles. Reaction is very slow. Reaction= hours. Thinner solu. than HOHO resin.

Note D-Reaction time in all examples 2 to 3 hours except where otherwise indicated.

1 It is quite possible that in a molal ratio of 1, 4 and 5 that not more than 4 moles of the aldehyde enters into reaction particularly when an acid catalyst is used. For this reason the value of .8 for example in column 3 corresponding to Examples 200 and 2111 may still well be theoretical 100% combination.

4 Theoretical molecular weight based on the single structural unit.

3 Viscosity taken as solution in high boiling solvent.

PART 2 As noted previously, a variety of secondary amines free from a primary amino group may be employed. These The resins illustrated by Examples la through 22a have 5 been prepared using bisphenol B instead of bisphenol A. The products obtained were substantially identical except that y Seem to Show a little higher Oil Solubility and amines fall into five categories, as indicated previously. 165$ tendency, if y, towards formation The Same One category consists of strongly basic secondary monois true Where bisphenol C has 76911 p y A amines tree from hydroxyl groups whose composition may ture of materials consisting of 3,5 Xylenol, m-ethyl phenol, b i di d h m-cresol was subjected to reaction with an acetone to give a cogeneric mixture of bisphenols which appear to be perfectly satisfactory when substituted for bisphenol A in NH the above examples. R

9 in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic in a few instances as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylarnine, methylethylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylarnine, diamylamine, dihexylamine, dioctylamine, and dinonylamine, Other amines include bis(1,3-dimethylbutyl) amine. There are, of course, a variety of primary amines which can be reacted With an alkylating agent such as dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alphamethylbenzylamine, or benzylamine itself, to produce a suitable reactant. Needless to say, one can use secondary amines such as dicyclohexylamine, dibutylamine or amines containing one cyclohexyl group and one alkyl group, or one benzyl group and one alkyl group, such as ethylcyclohexylamine, ethylbenzylamine, etc.

Other suitable compounds are exemplified by Other somewhat similar secondary amines are those of the composition as described in US. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, popyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in US. Patent No. 2,482,546 dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta-phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by The secondary category represents secondary amines which are hydroxylated monoamines. These may be illustrated by diethanolamine, methylethanolamine, dipropanolamine, dibutanolamine and ethylpropanolamine. Suitable primary amines which can be so converted into secondary amines include butylamine, amylamine, hexylamine, higher molecular Weight amines derived from fatty acids, cyclohexylamine, benzylamine, furfurylamine, etc.

Other suitable amines include Z-amino-l-butanol, 2- amino Z-methyl -1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3propanediol, and tris-(hydroxylmethyl)-aminoethane. Another example of such amines is illustrated by 4-amino-4-methyl-2-pentanol.

Other suitable compounds are the following:

(CgHgOCIHlOCzHg) (021160 011140 (1311 0 CjHl) (CIHDO CHICH(CHI) 0 (CH1) CHCHI) NH HOC1H (CH 0 CHzGHgO CHiCHtO CH CH2) HO C2114 amine, such as N-hydroxyethylfructamine.

Other suitable amines may be illustrated by GHs.C.GH2OH NH CHa.( 3.CH2OH JH:

See also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in US. Patent No. 2,510,063, dated June, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with a mole of an oxyalkylating agent as described; phenoxyethylamine, phenoxyalphamethylethylamine, and phenoxypropylamine.

Polyamines free from a hydroxyl group may be illustrated by the following:

NpropyleneNpropyleneN on, on NoinrNciniNoiniNcimN H H H \H NpropyleneNpropyleneN H O C 2H4 BO C2114 can on NC zHaNCsHtN CZHANCiHtN H H H CH1 CH Z-undecylimidazoline Z-heptadecylimidazoline 2-oleylimidazoline 1-N-decylaminoethyl,Z-ethylimidazoline Z-methyl, 1-hexadecylaminoethyla-minoethylimidazoline 1-dodecylaminopropylimidazoline 1- (stearoyloxyethyl) amino ethylimidazoline l-stearamidoethylaminoethylimidazoline 1- (n-dodecyl) -acetamidoethylaminoethylirnidazoline 2-heptadecyl, 4,5-dimethylimidazoline 1-dodecylaminohexylimidazoline 1-stearoyloxyethylaminohexylimidazoline Z-heptadecyl, l-methylaminoethyl tetrahydropyrimidine 4-methyl,2dodecyl,l-methylaminoethylaminoethyl tetrahydropyrimidine As to hydroxylated reactants all that is required is to employ a suitable compound having a 5-membered ring or after being subjected to oxyalkylation with ethylene oxide or the like. Thus, a compound having no basic secondary amino radical but a basic primary amino radical can be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described condensation procedure. This can be illustrated in the following manner by a compound such as 2-heptadecyl,l-aminoethylimidazoline which can be reacted with a single mole of ethylene oxide, for example to produce the hydroxy ethyl derivative of Z-heptadecyl,l-aminoethylimidazoline, which can be illustrated by the following formula:

Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, 2- heptadecyl,l-arninoethylimidazoline; for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. If reacted with ethylene imine the net result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amine group. If ethylene imine is employed, the net result is simply to convert Z-heptadecyl, l-aminoethylimidazoline into Z-heptadecyl, l-diethylenediarn neimidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i.e., one having both ethylene groups and a propylene group between nitrogen atoms,

PART 3 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

The herein described amine-modified resins are obtained from formaldehyde or in some instances glyoxal and resins of the kind described in Part 1 preceding, in combination with secondary amines. Generally speaking in the preparation of conventional amine-modified resins the object is to obtain a heat-convertible compound or resin or at least heat convertible in presence of added formaldehyde. See, for example, US Patent No. 2,031,557 to Bruson. Since the condensation products obtained in the present invention are not heat-convertible and since temperature up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps, no description is necessary over and above what has been previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind de scribed in aforementioned US. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid, but is apt to be a solid even at higher temperatures than usual or ordinary room temperature. Thus, I have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance at 150 C. or thereabouts. A suitable solvent is usually benzene, xylene or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent of the kind noted, and it is not necessary to have a single phase system for reaction.

Needless to say, the resins used are tetrafunctional. They could be combined with one mole of an appropriate amine or with 2 moles or with 3 moles or with 4 moles. If combined with one mole, or with 2 moles of an appropriate amine there is no advantage in using the previously described resins over the conventional resins derived from difunctional phenols only. The real advantage is the ability to combine at least 3 and more particularly 4 moles of amine with one mole of a resin having a total of 3 to 6 phenolic nuclei. For this reason the hereto appended claims specifically limit my invention to such combinations where at least 3 moles of appropriate amine is combined with 1 phenolic resin.

In the preparation of resin condensates the aldehydes used are formaldehyde and glyoxal. The use of glyoxal is limited to such compounds wherein solubility does not occur. Needless to say, when glyoxal is used to obtain substantially the same effect, the molar ratio is cut in two. In the claims reference is made to formaldehyde as such, but obviously where glyoxal can be substituted such products would be within the boundaries of the inyention.

Although the condensation reaction can be conducted without the use of a solvent, in fact, it can be conducted using formaldehyde in high concentrations or even the anhydrous equivalent, it is preferred to use the 37% solution and also to use a solvent.

I have found no difficulty in promoting the condensation reaction although at times it is desirable to add some solvent having a common solvent effect. Thus an oxygenated solvent may or may not be employed. Such solvent may be employed in combination with a hydrocarbon solvent such as xylene. However, if the reaction mass is going to be subjected to some further reaction A where the solvent may be objectionable as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohols should not be used or else it should be removed. The fact that an 14 oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscouse liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the condensation products obtained are invariably dark and particularly reddish or dark red in color.

In some instances condensates have been prepared using a formaldehyde in one case and glyoxal in the other. Due to the difunctional property of glyoxal the condensate frequently is harder and at times may even be insoluble.

Indeed, depending on the resin selected and the amine selected the condensate product or reaction mass on a solvent-free basis is apt to be harder than the original resin itself. This is particularly true when all the amino hydrogen atoms present in the amine have entered into reaction, as in the case of a polyamine.

The products obtained, depending on the reactants selected, may be water-insoluble, or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxy-acetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amounts of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

It so happens as will be pointed out that frequently it is convenient to eliminate all solvent using a temperature of not over C. and employing vacuum if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene xylene, or the like, depends primarily on cost, i.e., the use of the most economical solvent and also on three other factors, two of which have been mentioned previously; (a) is the solvent to remain in the reaction mass without removal; (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor is this; (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a waterwash to remove any unreacted low molal soluble amine, if employed and present after reaction? Such procedures are well known, and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no advantage in using a low temperature, approximately room temperature, at the start of the reaction although this is sometimes done purely as a matter of convenience. Indeed, using formaldehyde I have usually done nothing more than prepare the reaction mixture, add a suitable amount of xylene, and reflux for approximately 1 /2 to 6 /2 hours at temperatures varying, as the case may be, from 135 to C. Where the amine has a comparatively low basicity I have sometimes added a small amount or approximately 1% of sodium methylate.

However, using a xylene-benzene mixture, for instance, approximately 17 parts of benzene and 35 parts of xylene, and a phase-separating trap to eliminate water I have found that I could employ temperatures between 90 and 100 C., and eliminate the water of condensation by refluxing at this temperature. However, I have found no particular advantage in using this intermediate temperature over and above the high temperature previously noted.

The only bisphenol commercially available at quantity prices is bisphenol A. The four most readily available difunctional phenols having alkyl groups of at least four carbon-atoms or more are: p-tertiary-amyl phenol, p-tertiary-butyl phenol, octyl phenol and nonyl phenol. The cheapest aldehyde and most suitable aldehyde is formaldehyde. For this reason the description of the condensation reaction has been limited to these products which best serve as raw material in actual commercial manufacture. Thus, the resins employed in the subsequent examples and tables are 1a, 18a, 19a and 20a. The latter was made from bisphenol B.

Generally speaking, the preference has been to prepare condensates which had substantial hydrophile properties. This usually means the use of hydroxylated amines or polyamines. Those commercially available and particularly suitable include: diethanolamine, diisopropanolamine, dibutanolamine and the polyamines which have been reacted with approximately 2 mols of an alkylene oxide such as ethylene oxide. Such compounds include among others symmetrical di(hydroxyethyl) ethylene diamine, symmetrical di(hydroxyethyl) diethylene triamine, symmetrical di(hydroxypropyl) ethylene diamine, symmetrical di(hydroxybutyl) ethylene diamine and the comparable products derived from 1,2 diaminopropane or 1,3 diaminopropane. From a practical standpoint most readily available amines include diethanolamine, diisopropanolamine, symmetrical di(hydroxyethyl) ethylene diamine, morpholine, etc. Using diamines, and especially a polyamine having a single reactive secondary amine group such as the hydroxyethyl derivative of dimethylamino propylamine obtained by the reaction of one mol of ethylene oxide and one mol of dimethylamino propylamine yields condensates, which are particularly suitable for the present purpose. Another particularly suitable amine is alpha-methylbenzyl monoethanolamine.

It is not necessary to point out that in the condensation reaction one may obtain condensates which in all likelihood are monomers particularly when derived from a monoamino reactant such as diethanolamine or diisopropanolamine. On the other hand when derived from diamines in which there are two secondary amino groups available for reaction obviously more complex forms and probably polymers may form. This may apply also where glyoxal is used.

16 The complexity of structure is increased if one employs a symmetrically substituted polyamine such as di(hydroxyethyl) 'diethylenetriarnine or triethylenetetramine or synmietrical di(hydroxyethyl) 3,3-iminobispropylamine. In making a large variety of condensates I employed conventional glass pots with appropriate heating jackets, condensers, and stirrers, etc. These glass pots had a capacity of approximately 5 liters. The procedure employed is illustrated by the example immediately follow- Example 1b 954 grams of the resin identified as la was dissolved in approximately 422 grams of xylene. To this was added 420.6 grams of diethanolamine. After mixing at room temperature 324.5 grams of 37% formaldehyde was added slowly and the temperature raised over a period of time to approximately 140 C. and the mixture was allowed to reflux for about 2 to 3 hours. During this period of time water of solution or water of reaction was withdrawn so that the mixture continued to reflux to 148 for another hour. In some instances some xylene was withdrawn and some benzene added to hold the temperature in the approximate 145 to 150 range. Actually, the completion of condensation can be determined readily by continuing until no more water can be separated by means of a conventional phase separating trap. In the final product xylene was returned to the mass if required or enough of the solvent was distilled out so that the solvent remaining behind was the same as originally added. This was purely for a matter of convenience in order that the mixture as completed contained the same amount of solvent as when it started. In each instance a small amount of sample was heated to eliminate the xylene or other solvent. The resultant product was usually hard or sometimes tacky rather than hard and the color varied from reddish black to almost black. In some instances the condensate was amber or dark brown rather than reddish. The product so obtained could be bleached with the filtering chars or filtering earths. For most purposes, and particularly when used subsequently as chemical reactant, there is no advantage in such bleaching. In such instances where there was a tendency to form insoluble or semi-rubbery masses, there is some advantage in using an oxygen-containing solvent such as the dimethyl ether of diethylene glycol. Such solvent was used to replace the third or fourth of the xylene or benzene. 7

Similar products were prepared as indicated in the following tables:

NOTE.III the above table AA is used to designate diethanolamine; BB is used to designate diisopropanolamine; CO is used to designate alpha methylbenzylmonoethanolamine; DD is used to designate hydroxyethyl dirnethylamino propylamine obtained by reaction between 1 mole of ethylene oxide and 1 mole of dimethylamino propylamine.

TABLE IV Reaction data Molal ra- Ratio tio of Water water Ex. No. reactant out, out to Theo. resin: grams aldehy. Max. Time pe- Char. of solventmolee. amine present temp. riod Color of product free condensate weight aldehyde per structural unit 1: 4 270. 0. 92 148 2% Dk. amber Hard brittle"-.- 1, 422 1: 4 272. 4 0.95 146 2% Dk purple do 1, 356 1' 4 269. 5 0. 91 149 481 4 268 0. 89 149 1, 641 1: 4 273 O. 96 144 1, 534 1: 4 271.7 0. 94 146 1, 468 1: 4 268. 8 0. 90 148 1, 593 1: 4 269. 5 0. 91 145 1, 753 1: 4 267. 3 0. 88 147 1, 663 1: 4 268. 7 0. 90 147 1, 597 1: 4 271 0. 93 145 1, 722 1: 4 265.2 0.85 144 1, 882 1: 4 266. 6 0. 87 147 1, 539 1: 4 270. 5 0. 92 149 1, 473 1: 4 267. 3 0. 88 143 1, 598 1: 4 264. 5 0. 84 146 1, 758 1: 2 322 0. 68 144 1, 423 1: 2 325 0. 75 142 1, 468

There is no need to conduct the resinification in one piece of equipment and the condensation in another piece of equipment. Condensation in this instance refers to the reaction involving the amine. Of course, resinification in the manufacturing of phenol-aldehyde resins is obviously a condensation reaction. Thus, one can use a large size glass pot about 5 liters capacity, add the bisphenol such as bisphenol A along with the selected catalyst such as diamyl naphthalene sulfonic acid together with the solvent. Formaldehyde can be added in appropriate fashion. When resinification is complete and water of solution or water of reaction has been withdrawn by means of a phase separating trap the reaction mass can be cooled, and the selected amine such as diisopropanolamine can be added after having previously added suificient caustic soda to neutralize the sulfonic acid. Formaldehyde can then be added and the second one of the condensation reactions can be conducted in the same equipment and thus simplify manufacturing procedures. Actually, this is the procedure employed on a larger scale in actual manufacture.

It has been previously pointed out that the structure of the condensate may vary considerably and as may be monomeric and polymeric. Note also what has been said in the introductory part of the specification in regard to the combinations possible in complexity of the structure of various condensates.

PART 4 As to the use of conventional demulsifying agents reference is made to US. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with-equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 1b, herein described.

PART 5 The products described in Part 4 have utility in at least two distinct waysthe products as such, or in the form of some simple derivative, such as the salt which can be used in numerous arts subsequently described. Also, the products can serve as initial materials for more complicated reactions of the kind previously mentioned, to Wit, they may be subjected to oxyalkylation, particularly oxyethylation, or oxypropylation or oxybutylation to give products which are not only valuable for the purpose described in regard to the parent material or the salts of the parent material, but also for other purposes. Likewise, since the tertiary amino nitrogen atom is present the products can readily be reacted with suitable reactants such as chloroacetic acid esters, benzylchloride, alkyl halides, esters of sulfonic acids, methyl sulfate or the like, to give quaternary ammonium compounds which are used, not only for the purpose herein described, but also for various other uses.

In such instances where the amine contains a hydroxyl group the product is susceptible to reactions involving the hydroxyl radical, particularly acylation reactions, etc., i.e., reactions involving the use of either monocarboxy acids which may be low molal or high molal, and polycarboxy acids of the kind previously enumerated.

The products herein described as such and prepared in accordance with this invention can be used as emulsifying agents, for oils, fats and waxes, as ingredients in insecticides compositions, or as detergents and Wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They also may be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Other uses include the preparation or resolution of petroleum emulsions, whether of the water-in-oil type or oil-in-water type. They may be used as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts. They may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop microorganic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type. Some have definite anti-corrosive action. They may be used in connection with other processes where they are injected into an oil or gas well for the purpose of removing a mud sheath, increasing the ultimate flow or fluid from the surrounding strata, and particularly in the secondary recovery operations using aqueous flood waters. They may be used also in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials as such, or in the form of a salt; the salt form refers to a salt involving either one or both basic nitrogen atoms. Obviously, the salt form involves a modification in which the hydrophile character can either be increased or decreased and, inversely, the hydrophobe character can be decreased or increased. For example, neutralizing the product with practically any low molal acid, such as acetic acid, hydroxy acetic acid, lactic acid, or nitric acid, is apt to markedly increase the hydrophile effect. One may also use acids of the type in which R is a comparatively small alkyl radical, such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophobe eifect increased by neutralization with a monocarboxy detergent-forming acid. These are acids which have at least 8 and not more than 32 carbon atoms. They are obtained from higher fatty acids and include also resin acids such as abieticacid, and petroleum acids such as naphthenic acids and acids obtained by the oxidation of wax. One can also obtain new products having unique properties by combination With polybasic acids, such as diglycolic acid, oxalic acid, dimerized acids from linseed oil, etc. The most common examples, of course, are the higher fatty acids having generally 10 to 18 carbon atoms. I have found that a particularly valuable anti-corrosive agent can be obtained from any suitable resin and formaldehyde provided the secondary amine is hydroxyethyl cyclohexylamine. The corrosion inhibiting properties of this compound can be increased by neutralization with either one or tWo moles of an oilsoluble sulfonic acid, particularly a sulfonic acid of the type known as mahogany sulfonic acid. I have found the products herein described are of unusual utility for preventing the separation of sludge in fuel oil during storage. These products are also valuable as antioxidants for use in gasoline and various fuels in ratios of 10 to 50 ppm.

See also my co-pending application, Serial No. 448,174, filed August 6, 1954.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is 1. The process of condensing (a) an oxyalkylation-susceptible, fusible organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule wherein one phenolic nucleus is a bisphenol nucleus and the other phenolic nuclei are alkyl phenol nuclei; said resin being derived by reaction between an aldehyde having not over 8 carbon atoms and a mixture composed of two types of phenols, one being (A) a phenol of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; the other being (B) a bisphenol nuclearly tetrafunctional with respect to aldehydes, containing from 13 to 23 carbon atoms and composed exclusively of carbon, hydrogen and oxygen atoms; the molar ratio of the two types of phenols in the mixture reacted with the aldehyde being so as to contribute one bisphenol nucleus per resin molecule;

(b) a basic secondary amine composed only of carbon, hydrogen, oxygen and nitrogen atoms free from any primary amino radical, having up to 32 carbon atoms and reactive towards formaldehyde, the nitrogen atom of the secondary amine being directly attached by single bonds to two different carbon atoms neither of which is a member of an aromatic ring;

(c) formaldehydes; said condensation reaction being conducted'at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; the molar ratio of reactants (a), (b) and (0) being approximately within the range of 13:3 to 124:4 respectively; and the resinous condensation product resulting from the process being heatstable and oxyalkylation-susceptible.

2. The process of claim 1 in which the basic secondary amine reactant (b) has an alkanol radical attached to one secondary amino nitrogen atom.

3. The process of condensing (a) an oxyalkylation-susceptible, fusible, organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular Weight corresponding to at least 3 and not over 5 phenolic nuclei per 1 resin molecule wherein one phenolic nucleus is a bisphenol nucleus and the other phenolic nuclei are alkyl phenol nuclei; said resin being derived by reaction between formaldehyde and a mixture composed of two types of phenols, one being (A) a phenol of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; the other being (B) a bisphenol nuclearly tetrafunctional with respect to aldehydes, containing from 13 to 23 carbon atoms and composed exclusively of carbon, hydrogen and oxygen atoms; the molar ratio of the two types of phenols in the mixture reacted with the aldehyde being so as to contribute one bisphenol nucleus per resin molecule;

(b) a basic hydroxylated secondary amine composed only of carbon, hydrogen, oxygen and nitrogen atoms free from any primary amino radical, having up to 32 carbon atoms, having two to four alkanol radicals which in turn have not over 8 carbon atoms in any alkanol radical and reactive towards formaldehyde, the nitrogen atom of the secondary amine being directly attached by single bonds to two diiferent carbon atoms neither of which is a member of an aromatic rlng;

(0) formaldehyde; said condensation reaction being conducted at a temperature within the range of about to C.; the molar ratio of reactants (a), (b) and (0) being approximately 1:4:4 respectively, the condensation reaction being carried out while the reactants (a), (b) and (c) are in admixture with an inert solvent and the resinous condensation product result- 7 ing from the process being heat-stable and oxyalkylation-susceptible.

4. The product resulting from the manufacturing process defined in claim 1.

5. The product resulting from the manufacturing process defined in claim 3.

References Cited in the file of this patent UNITED STATES PATENTS 2,031,557 Bruson Feb. 18, 1936 2,330,217 Hunn Sept. 28, 1943 2,564,191 De Groote et al. Aug. 14, 1951 2,679,485 De Groote May 25, 1954 2,695,888 De Groote Nov. 30, 1954 

1. THE PROCESS OF CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE WHEREIN ONE PHENOLIC NUCLEUS IS A BISPHENOL NUCLEUS AND THE OTHER PHENOLIC NUCLEI ARE ALKYL PHENOL NUCLEI, SAID RESIN BEING DERIVED BY REACTION BETWEEN AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND A MIXTURE COMPOSED OF TWO TYPES OF PHENOLS, ONE BEING (A) A PHENOL OF THE FORMULA 